CN104508048A - Hardening composition - Google Patents

Abstract

The present invention relates to curable compositions and their use. An example of a curable composition has excellent handleability and processability. In addition, the curable composition exhibits excellent light extraction efficiency, hardness, thermal shock resistance, moisture resistance, air permeability, and adhesiveness when cured. In addition, the curable composition exhibits reliable durability even under severe conditions for a long time without whitening or surface tackiness.

Description

curable composition

technical field

The present application relates to curable compositions and uses thereof.

Background technique

Light-emitting diodes (LEDs), for example, particularly blue or ultraviolet (UV) LEDs having an emission wavelength of about 250 nm to 550 nm, are high-brightness products using GaN-based compound semiconductors such as GaN, GaAlN, InGaN, or InAlGaN. In addition, it can form high-quality full-color images by combining red and green LEDs with blue LEDs. For example, a technique of manufacturing white LEDs by combining blue LEDs or UV LEDs with fluorescent materials is known.

Such LEDs are widely used as backlights for liquid crystal displays (LCDs) or as lighting.

Epoxy resins with high adhesion and excellent mechanical durability are widely used as LED encapsulants. However, epoxy resins have low light transmittance in the blue or ultraviolet region and low heat resistance and light resistance. For example, Patent Documents 1 to 3 and the like propose techniques for solving the above-mentioned problems. However, the encapsulants disclosed in the above documents do not exhibit sufficient heat resistance and light resistance.

[current technology]

Patent Document 1: Japanese Patent Laid-Open No. H11-274571

Patent Document 1: Japanese Patent Publication No 2001-196151

Patent Document 1: Japanese Patent Laid-Open No. 2002-226551

Contents of the invention

technical problem

The present application provides curable compositions and uses thereof.

solution

One aspect of the present application provides a curable composition comprising a component curable by hydrosilylation (eg, a reaction between an aliphatic unsaturated bond and a hydrogen atom). For example, the curable composition may include a polymerization product including a polyorganosiloxane having a functional group including an aliphatic unsaturated bond (hereinafter referred to as “polyorganosiloxane (A)”).

The term "M unit" used herein may refer to a monofunctional siloxane unit represented as (R ₃ SiO _1/2 ) in the art, and the term "D unit" used herein may refer to a monofunctional siloxane unit in the art The difunctional siloxane unit which can be expressed as (R ₂ SiO _2/2 ) in the term "T unit" as used herein can refer to the trifunctional siloxane unit which can be expressed as (RSiO _3/2 ) in the art alkane unit, and the term "Q unit" as used herein may refer to a tetrafunctional siloxane unit which may be expressed as (SiO _4/2 ) in the art. Here, R is a functional group bonded to a silicon atom and may be, for example, a hydrogen atom, a hydroxyl group, an epoxy group, an alkoxy group, or a monovalent hydrocarbon group.

The polyorganosiloxane (A) may have, for example, a linear structure or a partially crosslinked structure. The term "linear structure" may refer to the structure of polyorganosiloxane composed of M units and D units. In addition, the term "partially crosslinked structure" may refer to a sufficiently long linear structure of polyorganosiloxane derived from D units and partially introduced with T or Q units (eg, T units). In one embodiment, the polyorganosiloxane having a partially crosslinked structure may refer to the ratio of D units to all D, T, and Q units contained in the polyorganosiloxane (D/(D+T+Q) ) is 0.65 or greater polyorganosiloxane.

In one embodiment, the polyorganosiloxane (A) having a partially crosslinked structure may contain a D unit and a T unit which share one oxygen atom and are connected to each other. The connected unit can be represented by Formula 1, for example.

[Formula 1]

In Formula 1, ^R4 and ^R5 are each independently an alkyl group, an alkenyl group or an aryl group, and ^R6 is an alkyl group or an aryl group. In Formula 1, both R ⁴ and R ⁵ may, for example, be an alkyl group or an aryl group at the same time.

The polyorganosiloxane (A) having a partially crosslinked structure may contain at least one unit of formula 1 . The unit of formula 1 is such a type that the silicon atom of the D unit is directly linked to the silicon atom of the T unit via the oxygen atom between the siloxane units forming the polyorganosiloxane (A). For example, as will be described later, the polyorganosiloxane (A) including the unit of Formula 1 can be produced by polymerizing (for example, ring-opening polymerization) a mixture including a cyclic siloxane compound. When this method is applied, a polyorganosiloxane comprising a unit of Formula 1 and having a minimum number of alkoxy-bonded silicon atoms and hydroxyl-bonded silicon atoms in its structure can be prepared.

The polyorganosiloxane (A) may contain at least one functional group containing an aliphatic unsaturated bond, for example at least one alkenyl group. For example, the molar ratio (Ak/Si) of aliphatic unsaturated bond-containing functional groups (Ak) to all silicon atoms (Si) in polyorganosiloxane (A) may be, for example, about 0.01 to 0.2 or 0.02 to 0.15. When the molar ratio (Ak/Si) is controlled to be 0.01 or more, or 0.02 or more, reactivity can be properly maintained and leakage of unreacted components from the surface of the cured product can be prevented. In addition, when the molar ratio (Ak/Si) is controlled to be 0.2 or less, or 0.15 or less, the crack resistance of the cured product can be excellently maintained.

The polyorganosiloxane (A) may contain aryl groups, for example at least one aryl group bonded to a silicon atom. For example, when the polyorganosiloxane (A) has a linear structure, the aryl group can be linked to the silicon atom of the D unit, and when the polyorganosiloxane (A) has a partially crosslinked structure, the aryl group can be linked to the D unit and/or the silicon atoms of the T unit are connected. In addition, in the polyorganosiloxane (A), the ratio of the molar number of aryl groups (Ar) to the number of moles of all functional groups connected to silicon (R) may be a percentage of about 30% to 60% (100×Ar/R ). In another example, the ratio (Ar/ Si) may be, for example, 0.3 or more and less than 0.65. Within this range, the composition may have excellent handleability and workability before curing, and excellently maintain moisture resistance, light transmittance, refractive index, light extraction efficiency, hardness, etc. after curing. In particular, when the percentage (100×Ar/R) is kept at 30% or more, the mechanical strength and air permeability of the cured product can be properly ensured, and when the percentage is kept at 65% or less, excellent Crack resistance of the cured product.

The polyorganosiloxane (A) may contain a unit of formula 2 and a unit of formula 3 as D units.

[Formula 2]

(R ¹ R ² SiO _2/2 )

[Formula 3]

(R ³ ₂ SiO _2/2 )

In Formula 2 and Formula 3, R ¹ and R ² are each independently an epoxy group or a monovalent hydrocarbon group, and R ³ is an aryl group. In one embodiment, R ¹ and R ² are each independently alkyl.

Unless otherwise specifically defined, the term "monovalent hydrocarbon group" as used herein may refer to a monovalent residue derived from an organic compound composed of carbon and hydrogen or a derivative thereof. For example, a monovalent hydrocarbyl group may contain 1 to 25 carbon atoms. The monovalent hydrocarbon group may be an alkyl, alkenyl, alkynyl or aryl group.

Unless otherwise specifically defined, the term "alkyl" as used herein may refer to an alkyl group having 1 to 20, 1 to 16, 1 to 12, 1 to 8, or 1 to 4 carbon atoms. Alkyl groups can have a linear, branched or cyclic structure. In addition, the alkyl group may be optionally substituted with at least one substituent.

Unless otherwise specifically defined, the term "alkenyl" as used herein may refer to an alkenyl group having 2 to 20, 2 to 16, 2 to 12, 2 to 8, or 2 to 4 carbon atoms. Alkenyl groups may have a linear, branched or cyclic structure, and may be optionally substituted with at least one substituent.

As used herein, unless specifically limited otherwise, the term "alkynyl" may refer to an alkynyl group having 2 to 20, 2 to 16, 2 to 12, 2 to 8, or 2 to 4 carbon atoms. Alkynyl groups can have linear, branched or cyclic structures. and may be optionally substituted with at least one substituent.

Unless otherwise specifically defined, the term "aryl" as used herein may refer to a compound derived from a compound containing benzene rings or wherein at least two benzene rings are fused or connected by a covalent bond having 1 or 2 carbon atoms. A monovalent residue of a compound of structure, or a derivative thereof. Within the scope of aryl groups, functional groups conventionally known as aralkyl groups or arylalkyl groups may also be included, in addition to functional groups conventionally known as aryl groups. Aryl groups may, for example, be aryl groups having 6 to 25, 6 to 21, 6 to 18 or 6 to 12 carbon atoms. Aryl can be phenyl, dichlorophenyl, chlorophenyl, phenethyl, phenylpropyl, benzyl, tolyl, xylyl or naphthyl.

Unless otherwise specifically defined, the term "epoxy group" as used herein may refer to a monovalent residue derived from a cyclic ether having three ring-forming atoms or a compound comprising a cyclic ether. The epoxy group may be glycidyl, epoxyalkyl, glycidoxyalkyl, or cycloaliphatic epoxy. The alicyclic epoxy group may refer to a monovalent residue derived from a compound including an aliphatic hydrocarbon ring structure and an epoxy group structure formed of two carbon atoms of the aliphatic hydrocarbon ring. The alicyclic epoxy group may be an alicyclic epoxy group having 6 to 12 carbon atoms, such as 3,4-epoxycyclohexylethyl.

As a substituent which may optionally be substituted for an epoxy group or a monovalent hydrocarbon group, a halogen such as chlorine or fluorine, a glycidyl group, an epoxyalkyl group, a glycidoxyalkyl group, an epoxy group such as an alicyclic ring Oxygen group, acryloyl group, methacryloyl group, isocyanate group, thiol group or monovalent hydrocarbon group, but the present application is not limited thereto.

The molar percentage (100×D3/D) of the siloxane unit (D3) of formula 3 contained in the polyorganosiloxane (A) relative to the molar number of all D units (D) is about 30% to 65%, or 30% to 60%. In such a range, excellent mechanical strength, no surface stickiness, and long-term light transmittance and durability by controlling humidity and air permeability can be secured.

The percentage of moles of siloxane units (D3) of formula 3 contained in polyorganosiloxane (A) relative to the moles of D units (DAr) containing aryl groups among all D units (100×D3 /DAr) is about 70% or greater, 80% or greater, or 90% or greater. In such a range, it is possible to provide a composition which has excellent handleability and workability before curing and which can maintain excellent mechanical strength, air permeability, moisture resistance, light transmittance, refraction after curing rate, light extraction efficiency and hardness. The upper limit of the percentage (100×D3/DAr) is not particularly limited, and it may be, for example, 100%.

In one embodiment, polyorganosiloxane (A) may have an average empirical formula of Formula 4.

[Formula 4]

(R ⁴ ₃ SiO _1/2 ) _a (R ⁴ ₂ SiO _2/2 ) _b (R ⁴ SiO _3/2 ) _c (SiO _4/2 ) _d

In Formula 4, R ⁴ is each independently an epoxy group or a monovalent hydrocarbon group, at least one of R ⁴ is an alkenyl group, and at least one of R ⁴ is an aryl group. For example, an alkenyl group and an aryl group may be contained to satisfy the aforementioned molar ratio.

The expression "polyorganosiloxane expressed as a certain average empirical formula" as used herein means that the polyorganosiloxane is a single component expressed as a certain average empirical formula, or a mixture of at least two components and a mixture The average composition of each component in is expressed as the average empirical formula.

In Formula 4, at least one of R ⁴ is alkenyl and at least one R ⁴ is aryl. For example, an alkenyl group and an aryl group may be contained to satisfy the aforementioned molar ratio.

In the average empirical formula of Formula 1, a, b, c, and d are each a molar ratio of siloxane units of polyorganosiloxane (A), and for example, a may be a positive number, b may be a positive number, c can be 0 or a positive number, and d can be 0 or a positive number. When the sum of the molar ratios (a+b+c+d) is adjusted to 1, a can be from 0.01 to 0.15, b can be from 0.65 to 0.97, c can be from 0 to 0.30 or 0.01 to 0.30, and d can be from 0 to 0.01. 0.2 and b/(b+c+d) may be 0.7 to 1. When the polyorganosiloxane (A) has a partially crosslinked structure, b/(b+c+d) may be about 0.65 to 0.97 or 0.7 to 0.97. When the ratio of the siloxane unit is controlled as described above, appropriate physical properties according to applications can be secured.

In another example, polyorganosiloxane (A) may have an average empirical formula of Formula 5.

[Formula 5]

(R ⁵ R ⁶ ₂ SiO _1/2 ) _e (R ⁷ R ⁸ SiO _2/2 ) _f (R ⁹ ₂ SiO _2/2 ) _g (R ¹⁰ SiO _3/2 ) _h

In the average empirical formula of Formula 5, R ⁵ to R ¹⁰ are each independently an epoxy group or a monovalent hydrocarbon group. Here, at least one of R ⁷ to R ⁹ and R ⁵ may be an alkenyl group, and at least one of R ⁷ to R ⁹ and R ⁵ may be an aryl group. For example, in the average empirical formula, ^R7 and ^R8 are each independently an alkyl group, and ^R9 may be an aryl group.

In the average empirical formula of formula 5, e, f, g and h are the molar ratio of each siloxane unit of polyorganosiloxane (A), e can be a positive number, f can be 0 or a positive number, g can be 0 or a positive number, and h can be 0 or a positive number. When the sum of the molar ratios (e+f+g+h) is adjusted to 1, e may be 0.01 to 0.15, f may be 0 to 0.97, or 0.65 to 0.97, and g may be 0 to 0.97, or 0.65 to 0.97 And h may be 0 to 0.30 or 0.01 to 0.30. Here, (f+g)/(f+g+h) may be 0.7 to 1, and when polyorganosiloxane (A) has a partially crosslinked structure, (f+g)/(f+g+h ) can be about 0.65 to 0.97 or 0.7 to 0.97. When the ratio of the siloxane unit is controlled as described above, appropriate physical properties according to applications can be secured.

In one embodiment, in the average empirical formula of Equation 5, neither f nor g can be 0. When neither f nor g is 0, f/g may be in the range of 0.3 to 2.0, 0.3 to 1.5, or 0.5 to 1.5.

The polymerization product comprising polyorganosiloxane (A) may be, for example, a ring-opening polymerization product of a mixture comprising cyclic polyorganosiloxane. The polymerization product may contain a cyclic compound such as a cyclic polyorganosiloxane having a weight average molecular weight (Mw) of 800 or less, 750 or less, or 700 or less, and the proportion of the cyclic compound may be 7% by weight or less, 5% by weight or less, or 3% by weight or less. The proportion of the cyclic compound may be, for example, 0% by weight or more, more than 0% by weight, or 1% by weight or more. By controlling the above ratio, a cured product having excellent long-term reliability and crack resistance can be provided. The term "weight average molecular weight" used herein may refer to a conversion value relative to standard polyethylene measured by gel permeation chromatography (GPC). Unless otherwise specifically defined, the term "molecular weight" as used herein may refer to a weight average molecular weight. The cyclic compound may be a component generated in ring-opening polymerization to be described later, and may remain in a desired ratio under conditions of ring-opening polymerization or by treatment of a polymerization product after ring-opening polymerization.

Cyclic compounds may include, for example, compounds represented by at least Formula 6.

[Formula 6]

In Formula 6, R ^a and R ^b are each independently an epoxy group or a monovalent hydrocarbon group, and R ^c is an aryl group. In one embodiment, each of R ^a and R ^b independently can be an alkyl group. In addition, in Formula 6, m may be 0 to 10, 0 to 8, 0 to 6, 1 to 10, 1 to 8, or 1 to 6, and n may be 0 to 10, 0 to 8, 0 to 6, 1 to 10, 1 to 8 or 1 to 6. Also, here, the sum (m+n) of m and n may be 2 to 20, 2 to 16, 2 to 14, or 2 to 12.

When the proportion of the low-molecular-weight cyclic component comprising the cyclic compound prepared in the above-described type is controlled as described above, characteristics such as long-term reliability and crack resistance can be further improved.

In the polyorganosiloxane (A) or a polymerization product containing it, in the spectrum obtained by ¹ H NMR, relative to the functional group (e.g. alkenyl group such as vinyl The peak area derived from the alkoxy group connected to the silicon atom may be 0.01 or less, or 0.005 or less, or 0. Within the above range, a suitable viscosity may be exhibited and other physical properties may be excellently maintained.

In one embodiment, the polyorganosiloxane (A) or a polymerization product comprising the same may have an acid value obtained by KOH titration of 0.02 or less, or 0.01 or less, or 0. Within the above range, an appropriate viscosity can be exhibited and other physical properties can also be maintained excellently.

In one embodiment, the polyorganosiloxane (A) or a polymerization product comprising the same may have a viscosity at 25°C of 500 cP or higher, 1000 cP or higher, or 5000 cP or higher. Within the above range, handleability and hardness can be properly maintained. The upper limit of the viscosity is not particularly limited and the viscosity may be, for example, 300000 cP or less, 200000 cP or less, 100000 cP or less, 90000 cP or less, 80000 cP or less, 70000 cP or less, or 65000 cP or less.

The molecular weight of the polyorganosiloxane (A) or a polymerization product containing it may be 800 to 50,000, or 1,000 to 30,000. In this range, moldability, hardness and strength may be properly maintained.

The polymerization product containing polyorganosiloxane (A) may be, for example, a ring-opening polymerization product of a mixture containing cyclic polyorganosiloxane.

When the polyorganosiloxane (A) has a partially crosslinked structure, the mixture may further contain, for example, a polyorganosiloxane having a cage or a partial cage structure or a polyorganosiloxane containing a T unit.

As the cyclic polyorganosiloxane compound, for example, a compound represented by Formula 7 can be used.

[Formula 7]

In Formula 7, R ^d and ^Re are each independently an epoxy group or a monovalent hydrocarbon group, and o is 3 to 6.

The cyclic polyorganosiloxane may further include the compound of Formula 8 and the compound of Formula 9.

[Formula 8]

[Formula 9]

In Formula 8 and Formula 9, R ^f and R ^g are each an epoxy group or an alkyl group, Rh and ^{R i are} each an epoxy group or an aryl group, p is a number from 3 to 6, and q is 3 to 6 number.

In Formulas 7 to 9, specific kinds of R ^f to R ⁱ or specific values of o, p, and q and the ratio of components in the mixture may be determined by the desired structure of the polyorganosiloxane (A).

When the polyorganosiloxane (A) has a partially crosslinked structure, the mixture may further contain, for example, a compound having an average empirical formula of Formula 10 or a compound having an average empirical formula of Formula 11.

[Formula 10]

[R ^j SiO _3/2 ]

[Formula 11]

[R ^k R ¹ ₂ SiO _1/2 ] _p [R ^m SiO _3/2 ] _q

In Formula 10 and Formula 11, R ^j , R ^k and R ^m are each independently an epoxy group or a monovalent hydrocarbon group, R ¹ is an alkyl group having 1 to 4 carbon atoms, p is 1 to 3 and q is 1 to 10.

In Formulas 10 and 11, specific kinds of R ^j to R ^m or specific values of p and q and the ratio of components in the mixture may be determined by the desired structure of the polyorganosiloxane (A).

When a cyclic polyorganosiloxane is reacted with a polyorganosiloxane having a cage or partial cage structure or a polyorganosiloxane containing a T unit, a polyorganosiloxane having a desired partially crosslinked structure of an appropriate molecular weight can be synthesized. organosiloxane. In addition, according to the method, by minimizing functional groups such as alkoxy groups or hydroxyl groups bonded to silicon atoms in polyorganosiloxane or a polymerization product containing the same, target products having excellent physical properties can be produced.

In one embodiment, the mixture may further include a compound represented by Formula 12.

[Formula 12]

(R ⁿ R ^o ₂ Si) ₂ O

In Formula 12, each of R ⁿ and R ^o is an epoxy group or a monovalent hydrocarbon group.

In Formula 12, the specific kind of monovalent hydrocarbon group or the mixing ratio in the mixture can be determined by the desired polyorganosiloxane (A).

The reaction of the components in the mixture can be carried out in the presence of a suitable catalyst. Accordingly, the mixture may further comprise a catalyst.

As the catalyst which may be contained in the mixture, for example, a base catalyst may be used. Suitable base catalysts may be, but are not limited to: metal hydroxides such as KOH, NaOH or CsOH; metal silanolates comprising alkali metal compounds and siloxanes; or quaternary ammonium compounds such as tetramethylammonium hydroxide, tetramethylammonium hydroxide, Ethyl ammonium hydroxide or tetrapropyl ammonium hydroxide.

The ratio of the catalyst in the mixture may be appropriately selected in consideration of desired reactivity, and for example, the ratio may be 0.01 to 30 parts by weight, or 0.03 to 5 parts by weight relative to 100 parts by weight of the total weight of the reaction product in the mixture. parts by weight. In this specification, unless otherwise specifically defined, the unit "parts by weight" means a weight ratio between components.

In one embodiment, the reaction can be performed under solvent-free conditions where no solvent is used or in the presence of a suitable solvent. As the solvent, any kind of solvent in which the reaction product in the mixture, that is, disiloxane or polysiloxane can be properly mixed with the catalyst without affecting reactivity can be used. Solvents can be, but are not limited to, aliphatic hydrocarbon based solvents such as n-pentane, isopentane, n-hexane, isohexane, 2,2,4-trimethylpentane, cyclohexane or methylcyclohexane ; aromatic solvents such as benzene, toluene, xylene, mesitylene, ethylbenzene or methylethylbenzene; ketone-based solvents such as methyl ethyl ketone, methyl isobutyl ketone, diethyl ketone, methyl n-propyl ketone, methyl n-butyl ketone, cyclohexanone, methylcyclohexanone, or acetylacetone; ether-based solvents such as tetrahydrofuran, 2-methyltetrahydrofuran, diethyl ether, n-propyl ether, isopropyl ether, di Glyme, two alkene, dimethyl di ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol monomethyl ether or propylene glycol dimethyl ether; ester-based solvents such as diethyl carbonate, methyl acetate, ethyl acetate , ethyl lactate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, or ethylene glycol diacetate; or amide-based solvents such as N-methylpyrrolidone, formamide, N-formaldehyde N-methylformamide, N-ethylformamide, N,N-dimethylacetamide or N,N-diethylacetamide.

A reaction of the mixture such as ring-opening polymerization can be performed by adding a catalyst to the reaction product. Here, the reaction temperature may be controlled within a range of, for example, 0°C to 150°C, or 30°C to 130°C. In addition, the reaction time can be controlled within a range of, for example, 1 hour to 3 days.

The curable composition may further include a crosslinkable polyorganosiloxane (hereinafter referred to as "polyorganosiloxane (B)"). The term "crosslinkable polyorganosiloxane" may mean that T units or Q units must be contained as siloxane units and that the ratio of D units to D, T and Q units (D/(D+T+Q)) is less than 0.65 polyorganosiloxane.

The crosslinkable polyorganosiloxane can have an average empirical formula of Formula 13.

[Formula 13]

(R ¹¹ ₃ SiO _1/2 ) _a (R ¹¹ ₂ SiO _2/2 ) _b (R ¹¹ SiO _3/2 ) _c (SiO _4/2 ) _d

In formula 13, R ¹¹ is each independently an epoxy group or a monovalent hydrocarbon group, at least one of R ¹¹ is an alkenyl group, at least one of R ¹¹ is an aryl group, a is a positive number, and b is 0 or a positive number , c is a positive number, and d is 0 or a positive number, b/(b+c+d) is less than 0.65, 0.5 or less, or 0.3 or less, and c/(c+d) is 0.8 or more Large, 0.85 or greater, or 0.9 or greater.

In Formula 13, at least one or two of R ¹¹ may be alkenyl. In one embodiment, alkenyl groups may be present in such an amount that the ratio of the number of moles of alkenyl groups (Ak) contained in the polyorganosiloxane (B) relative to the number of moles of all silicon atoms (Si) (Ak/ Si) is about 0.05 to 0.4, or 0.05 to 0.35. When the molar ratio (Ak/Si) is controlled to be 0.05 or more, reactivity can be excellently maintained and bleeding of unreacted components from the surface of the cured product can be prevented. In addition, when the molar ratio (Ak/Si) is controlled to be 0.4 or less, or 0.35 or less, the hardness, crack resistance, and thermal shock resistance of the cured product can be excellently maintained.

In Formula 13, at least one of R ¹¹ may be an aryl group. Therefore, the refractive index and hardness of the cured product can be effectively controlled. The aryl group may be present in such an amount that the ratio (Ar/Si) of the number of moles of aryl groups (Ar) contained in the polyorganosiloxane (B) to the number of moles of all silicon atoms (Si) is 0.5 to 1.5, or 0.5 to 1.2. When the molar ratio (Ar/Si) is controlled to be 0.5 or more, the refractive index and hardness of the cured product can be maximized. In addition, when the molar ratio (Ar/Si) is controlled to be 1.5 or less, or 1.2 or less, the viscosity and thermal shock resistance of the composition can be properly maintained.

In the average empirical formula of Formula 13, a, b, c, and d are the molar ratios of the respective siloxane units. For example, when the sum (a+b+c+d) thereof is adjusted to 1, a is 0.05 to 0.5, b is 0 to 0.3, c is 0.6 to 0.95 and d is 0 to 0.2. In order to maximize the strength, crack resistance and thermal shock resistance of the cured product, (a+b)/(a+b+c+d) can be controlled to 0.2 to 0.7 and b/(b+c+ d) is controlled to be less than 0.65, 0.5 or less, or 0.3 or less, and c/(c+d) can be controlled to be 0.8 or more, 0.85 or more, or 0.9 or more. Here, the lower limit of b/(b+c+d) is not particularly limited and may be 0, for example. In addition, here, the upper limit of c/(c+d) is not particularly limited and may be, for example, 1.0.

The polyorganosiloxane (B) may have a viscosity at 25° C. of 5,000 cP or higher, or 1,000,000 cP or higher, and thus may properly maintain handleability before curing and hardness after curing.

The molecular weight of the polyorganosiloxane (B) may be, for example, 800 to 20,000, or 800 to 10,000. When the molecular weight is controlled to be 800 or higher, the moldability before curing and the strength after curing can be effectively maintained, and when the molecular weight is controlled to be 20,000 or lower, or 10,000 or lower, the viscosity can be maintained at an appropriate level.

The method for producing polyorganosiloxane (B) may be, for example, a method for producing polysiloxane conventionally known in the art, or a method similar to the method for producing organosiloxane (A).

The polyorganosiloxane (B) may be contained in such an amount that, for example, the weight ratio of the polyorganosiloxane (A) to the mixture of the polyorganosiloxane (A) and the polyorganosiloxane (B) (A/(A+B)) is about 10 to 50. Within the above range, the strength and thermal shock resistance of the cured product can be excellently maintained, and surface stickiness can also be prevented.

The curable composition may further contain a silicon compound containing a hydrogen atom bonded to a silicon atom (hereinafter referred to as "silicon compound (C)"). The silicon compound (C) may have at least one or two hydrogen atoms.

The silicon compound (C) may serve as a crosslinking agent to crosslink the composition by reacting with the functional group containing an aliphatic unsaturated bond of the polyorganosiloxane. For example, crosslinking and curing can be performed by an addition reaction of a hydrogen atom of the silicon compound (C) with an alkenyl group of the polyorganosiloxane (A) and/or (B).

As the silicon compound (C), any of various silicon compounds containing a hydrogen atom (Si—H) bonded to a silicon atom in a molecule can be used. Silicon compounds (C) may, for example, be linear, branched, cyclic or crosslinkable polyorganosiloxanes. The silicon compound (C) may be a compound having 2 to 1000 silicon atoms and preferably 3 to 300 silicon atoms.

The silicon compound (C) may be, for example, a compound of formula 14 or a compound having an average empirical formula of formula 15.

[Formula 14]

R ¹² ₃ SiO(R ¹² ₂ SiO) _n SiR ¹² ₃

[Formula 15]

(R ¹³ ₃ SiO _1/2 ) _a (R ¹³ ₂ SiO _2/2 ) _b (R ¹³ SiO _3/2 ) _c (SiO ₂ ) _d

In Formula 14 and Formula 15, R ¹² is each independently hydrogen or a monovalent hydrocarbon group, at least two of R ¹² are hydrogen atoms, at least one of R ¹² is an aryl group, and n is 1 to 100. In addition, R ¹³ is each independently hydrogen or a monovalent hydrocarbon group, at least two of R ^{13 are hydrogen atoms, at least one aryl group in R 13 ,} a is a positive number, b is 0 or a positive number, and c is a positive number And d is 0 or a positive number. For example, when the sum (a+b+c+d) thereof is adjusted to 1, a is 0.1 to 0.8, b is 0 to 0.5, c is 0.1 to 0.8 and d is 0 to 0.2.

The compound of formula 14 is a linear siloxane compound having at least two hydrogen atoms attached to a silicon atom. In Formula 14, n may be 1 to 100, 1 to 50, 1 to 25, 1 to 10, or 1 to 5.

The compound represented by the average empirical formula of Formula 15 may be a polysiloxane having a crosslinked or partially crosslinked structure.

In one embodiment, the ratio (H/Si) of the number of moles of hydrogen atoms (H) bonded to silicon atoms contained in the silicon compound (C) to the number of moles of all silicon atoms (Si) may be about 0.2 to 0.8, or 0.3 to 0.75. When the molar ratio is controlled to be 0.2 or more, or 0.3 or more, the curability of the composition can be maintained extremely well, and when the molar ratio is controlled to be 0.8 or less, or 0.75 or less, the curability of the composition can be extremely maintained. Good retention of crack resistance as well as thermal shock resistance.

The silicon compound (C) may contain at least one aryl group, and thus at least one of R ¹² in Formula 14 or at least one R ¹³ in Formula 15 may be an aryl group. Therefore, the refractive index and hardness of the cured product can be effectively controlled. The aryl group may be present in such an amount that the ratio (Ar/Si) of the number of moles of the aryl group (Ar) contained in the compound (C) relative to the number of moles of all silicon atoms (Si) is about 0.5 to 1.5, or 0.5 to 1.3. When the molar ratio (Ar/Si) is controlled to be 0.5 or more, the refractive index and hardness of the cured product can be maximized, and when the molar ratio (Ar/Si) is controlled to be 1.5 or less, or 1.3 or When it is smaller, the viscosity and crack resistance of the composition can be properly maintained.

Compound (C) may have a viscosity at 25°C of 0.1 cP to 100000 cP, 0.1 cP to 10000 cP, 0.1 cP to 1000 cP, or 0.1 cP to 300 cP. Within the above viscosity range, the handleability of the composition and the hardness of the cured product can be excellently maintained.

In addition, the molecular weight of compound (C) may be less than 2000, less than 1000, or less than 800, for example. When the molecular weight is 1000 or more, the hardness of the cured product may deteriorate. The lower limit of the molecular weight of the compound (C) is not particularly limited and may be 250, for example. In the compound (C), the molecular weight may be the weight average molecular weight or conventional molecular weight of the compound.

The method for preparing compound (C) is not particularly limited, and a conventional method for preparing polyorganosiloxane known in the art, or a method similar to the method for preparing polyorganosiloxane (A) may be employed.

The content of the compound (C) can be selected in the range of about 0.5 to 2.0, or 0.7 to 1.5 in the ratio (H/Ak) of the hydrogen bonded to the silicon atom contained in the compound (C) The number of moles of atoms (H) is relative to all aliphatic unsaturated bond-containing functional groups (Ak) contained in the curable composition (for example, all contained in polyorganosiloxane (A) and/or (B) The ratio of moles of functional groups containing aliphatic unsaturated bonds such as alkenyl groups. Within the above range of the molar ratio (H/Ak), there can be provided a composition which exhibits excellent handleability and workability before curing and exhibits excellent crack resistance, hardness, thermal shock resistance after curing It is non-toxic and sticky and will not cause whitening or surface stickiness even under harsh conditions.

The curable composition may further include a polyorganosiloxane (hereinafter referred to as "polyorganosiloxane (D)") containing a functional group having an aliphatic unsaturated bond such as an alkenyl group and an epoxy group.

The polyorganosiloxane (D) can act, for example, as a tackifier to increase bond strength.

In one embodiment, polyorganosiloxane (D) can be represented by the average empirical formula of Formula 16.

[Formula 16]

(R ¹⁴ ₃ SiO _1/2 ) _a (R ¹⁴ ₂ SiO _2/2 ) _b (R ¹⁴ SiO _3/2 ) _c (SiO _4/2 ) _d

In formula 16, R ¹⁴ is each independently an epoxy group or a monovalent hydrocarbon group, at least one of R ¹⁴ is an alkenyl group, at least one of R ¹⁴ is an epoxy group, a, b, c and d are each independently is 0 or a positive number, (c+d)/(a+b+c+d) may be 0.2 to 0.7, and c/(c+d) may be 0.8 or more. For example, when the sum of molar ratios (a+b+c+d) is adjusted to 1, a may be 0 to 0.7, b may be 0 to 0.5, c may be 0 to 0.8 and d may be 0 to 0.2.

In Formula 16, at least one or two of R ¹⁴ may be alkenyl. In one embodiment, alkenyl groups may be present in such an amount that the ratio of the number of moles of alkenyl groups (Ak) contained in the polyorganosiloxane (D) relative to the number of moles of all silicon atoms (Si) (Ak/Si ) is 0.05 to 0.35, or 0.05 to 0.3. In such a molar ratio (Ak/Si), it is possible to provide a cured product that exhibits excellent reactivity to another compound, thereby having excellent adhesive strength and having excellent physical properties such as impact resistance .

In Formula 16, at least one of R ¹⁴ may also be an epoxy group. Therefore, the strength and scratch resistance of the cured product can be properly maintained and excellent adhesiveness can be achieved. The epoxy group may be present in such an amount that the ratio (Ep/Si) of the number of moles of epoxy groups (Ep) contained in the polyorganosiloxane (D) relative to the number of moles of all silicon atoms (Si) may be 0.1 or greater, or 0.2 or greater. In this molar ratio (Ep/Si), the crosslinked structure of the cured product can be properly maintained and the heat resistance and adhesiveness can also be excellently maintained. The upper limit of the molar ratio (Ep/Si) is not particularly limited and may be, for example, 1.0.

In the average empirical formula of Formula 16, a, b, c, and d are the molar ratios of the respective siloxane units, and when the sum thereof is adjusted to 1, a may be from 0 to 0.7, and b may be from 0 to 0.5, c may be from 0 to 0.8, and d may be from 0 to 0.2. Here, c and d cannot be 0 at the same time. In order to maximize the strength, crack resistance and thermal shock resistance of the cured product, (c+d)/(a+b+c+d) can be controlled to 0.3 to 0.7, and c/(c+ d) The control is 0.8 or greater. Here, the upper limit of c/(c+d) is not particularly limited and may be, for example, 1.0.

The polyorganosiloxane (D) may have a viscosity at 25° C. of 100 cP or higher, or 100,000 cP or higher, and thus may properly maintain handleability before curing and hardness after curing.

The molecular weight of polyorganosiloxane (D) may be, for example, 1000 or higher, or 1500 or higher. When the molecular weight is controlled to be 1000 or higher, or 1500 or higher, a cured product having excellent handleability and workability before curing and excellent crack resistance after curing can be provided, Thermal shock resistance and adhesion to substrates. The upper limit of the molecular weight is not particularly limited and may be, for example, 20,000.

The method for preparing polyorganosiloxane (D) is not particularly limited, and for example, conventional methods for preparing polyorganosiloxane known in the art, or similar to the method for preparing polyorganosiloxane (A) can be used Methods.

Polyorganosiloxane (D) can be formulated, for example, relative to 100 parts by weight of other compounds in the curable composition (such as polyorganosiloxane (A), polyorganosiloxane (B) and/or silicon compound (C )) is included in an amount of 0.2 to 10 parts by weight, or 0.5 to 5 parts by weight, based on the total weight. In the above range, adhesiveness and transparency can be excellently maintained.

The curable composition may further comprise a hydrosilylation catalyst. Hydrosilylation catalysts can be used to facilitate hydrosilylation reactions. Any conventional component known in the art may be used as the hydrosilylation catalyst. A platinum-based, palladium-based or rhodium-based catalyst may be used as the catalyst. In the specification, a platinum-based catalyst may be used in consideration of catalyst efficiency, and it may be, but not limited to, chloroplatinic acid, platinum tetrachloride, an olefin complex of platinum, an alkenylsiloxane complex of platinum, or a platinum-based catalyst. carbonyl complexes.

The content of the hydrosilylation catalyst is not particularly limited as long as the hydrosilylation catalyst is contained in a catalytic amount (ie, an amount capable of acting as a catalyst). Generally, the hydrosilylation catalyst may be used at 0.1 ppm to 100 ppm, and preferably at 0.2 ppm to 10 ppm based on the atomic weight of platinum, palladium or rhodium.

The curable composition may further comprise an adhesion promoter alone or in combination with polyorganosiloxane (D) to further enhance adhesion to various substrates. Tackifiers are components capable of improving self-adhesion to compositions or cured products and may improve self-adhesion especially to metals and organic resins.

The tackifier may be, but not limited to, a silane having at least one or two functional groups selected from alkenyl groups such as vinyl groups, (meth)acryloyloxy groups, hydrosilyl groups (SiH groups), epoxy groups, alkoxy, alkoxysilyl, carbonyl, and phenyl; or organosilicon compounds such as cyclic or linear siloxanes having 2 to 30 silicon atoms, or 4 to 20 silicon atoms. In the specification, one kind or at least two tackifiers may be additionally mixed.

The tackifier can be used in an amount of 0.1% of the total weight of other compounds (such as polyorganosiloxane (A), polyorganosiloxane (B) and/or silicon compound (C)) relative to 100 parts by weight of the curable composition. A content of parts by weight to 20 parts by weight is included in the composition, but the content may be appropriately changed in consideration of desired improvement in adhesiveness.

According to needs, the curable composition can also contain one or at least two of the following additives: reaction inhibitors, such as 2-methyl-3-butyn-2-ol, 2-phenyl-3-1 -butyn-2-ol, 3-methyl-3-penten-1-yne, 3,5-dimethyl-3-hexen-1-yne, 1,3,5,7-tetramethyl - 1,3,5,7-tetrahexenylcyclotetrasiloxane or ethynylcyclohexane; inorganic fillers such as silica, alumina, zirconia or titania; carbon-functional silanes, their partial hydrolysis-condensation products or siloxane compounds; thixotropic agents such as haze-phase silica which can be used in combination with polyethers; conductivity-providing agents such as Metal powders of silver, copper or aluminum or various carbon materials; and toners such as pigments or dyes.

The curable composition may further include a fluorescent material. In this case, the kinds of fluorescent materials that can be used are not particularly limited, and for example, conventional kinds of fluorescent materials applied to LED packages can be used to realize white light.

Another aspect of the present application provides a semiconductor component, such as an optical semiconductor component. Exemplary semiconductor elements may be encapsulated by an encapsulant comprising a cured product of the curable composition.

Examples of semiconductor elements encapsulated by an encapsulant include diodes, transistors, thyristors, photocouplers, CCDs, solid-phase image reading (pick-up) diodes, monolithic ICs, hybrid ICs, LSIs, VLSIs, or light-emitting diodes ( LED).

In one embodiment, the semiconductor element may be a light emitting semiconductor (LED).

LEDs can be formed by stacking semiconductor materials on a substrate. The semiconductor material may be, but is not limited to, GaAs, GaP, GaAlAs, GaAsP, AlGalnP, GaN, InN, AlN, InGaAlN, or SiC. In addition, as a substrate, sapphire, spinel, SiC, Si, ZnO, or GaN single crystal can be used.

In addition, in order to manufacture an LED, a buffer layer may be formed between the substrate and the semiconductor material, if necessary. GaN or AlN may be used as the buffer layer. The method of stacking the semiconductor material on the substrate may be, but not particularly limited to, MOCVD, HDVPE, or liquid growth. In addition, the structure of the LED may be, for example, a single junction including a MIS junction, a PN junction, and a PIN junction, a heterojunction or a double heterojunction. In addition, LEDs may be formed using a single quantum well structure or a multiple quantum well structure.

In one embodiment, the emission wavelength of the LED may be, for example, 250 nm to 550 nm, 300 nm to 500 nm, or 330 nm to 470 nm. The emission wavelength may refer to the main emission peak wavelength. When the emission wavelength of the LED is set within the above range, a white LED having a long lifetime, high energy efficiency, and high color expression can be obtained.

LEDs can be packaged using the composition. Additionally, encapsulation of LEDs may be performed using only the composition, and in some cases, additional encapsulants may be used in combination with the composition. When two kinds of encapsulants are used in combination, after encapsulation using the composition, the packaged LED may be further encapsulated with another encapsulant. Alternatively, the LED can be encapsulated with an additional encapsulant and then encapsulated with the composition. As another encapsulant, epoxy resin, silicone resin, acryl resin, urea resin, imide resin, or glass may be used.

In order to encapsulate the LED with the composition, for example, a method including injecting the composition into a mold in advance, dipping a lead frame to which the LED is fixed, and curing the composition may be used, for example. Alternatively, a method comprising injecting the composition into a mold with the LED inserted therein and curing the composition may be used. As a method of injecting the composition, injection through a dispenser, transfer molding, or injection molding can be used. In addition, as another encapsulation method, there may be included a method of dripping the composition on the LED, coating the composition by screen printing or using a mask and curing the composition; A method of setting the cup with the LED at its bottom and allowing the composition to cure.

In addition, the composition can be used as a die attach material to secure the LED to the end of a lead or package or as a passivation layer on the LED or as a package substrate, as desired.

When it is necessary to cure the composition, the curing is not particularly limited and can be carried out by, for example, keeping the composition at a temperature of 60° C. to 200° C. for 10 minutes to 5 hours, or at an appropriate temperature for an appropriate amount of time in two steps. or more steps.

The shape of the encapsulant is not particularly limited and may be, for example, a bullet lens, a planar shape, or a film shape.

In addition, further improvements in LED performance can be facilitated according to conventional methods known in the art. In order to improve performance, for example, a method of providing a reflective layer or a light collecting layer on the back surface of the LED, a method of forming a compensating color member on the bottom thereof, a method of absorbing light having a wavelength shorter than that of the main emission peak, etc. A method of layer placement on the LED, a method of encapsulating the LED and further molding the LED with a hard material, a method of inserting the LED into a through-hole to be fixed, or contacting the LED with a leaded component by flip-chip contact A method of extracting light from the direction of the substrate.

Optical semiconductors such as LEDs can be effectively applied to, for example, backlights of liquid crystal displays (LCDs), lamps, various sensors, light sources of printers and copiers, light sources of automotive meters, signal lamps, indicator lights, display devices, light sources of flat-type LEDs, displays , decorations or different kinds of lighting equipment.

Effect

The curable composition according to the present application has excellent handleability and processability. In addition, the curable composition has excellent light extraction efficiency, hardness, thermal shock resistance, moisture resistance, air permeability, and adhesiveness. In addition, the curable composition can exhibit long-term stable durability and reliability even under severe conditions without causing whitening or surface stickiness. The composition may exhibit excellent light extraction efficiency, crack resistance, hardness, thermal shock resistance, and adhesiveness after curing.

specific implementation plan

Hereinafter, the curable composition according to the present application will be described in further detail with reference to Examples and Comparative Examples, but the scope of the curable composition is not limited to the following Examples.

Hereinafter, the abbreviation "Vi" refers to vinyl, the abbreviation "Ph" refers to phenyl, the abbreviation "Me" refers to methyl and the abbreviation "Ep" refers to 3-glycidoxypropyl.

1. Evaluation of component characteristics

Component characteristics were evaluated using a 5050 LED package made from polyphthalamide (PPA). Specifically, the curable composition may be dispensed in a PPA cup, kept at 70° C. for 30 minutes, and then cured at 150° C. for 1 hour, thereby manufacturing a surface mount LED. Then, test according to the following method.

(1) Sulfur exposure test

The LED was put into a 200 L glass container, 0.2 g of sulfur powder was added thereto and the LED was kept at 70° C. for 40 hours. Then, the luminance was measured to calculate a decrease rate of luminance from the initial luminance, and the results were then evaluated according to the following criteria.

<Evaluation criteria>

A: The reduction rate of luminance is 15% or less relative to the initial luminance

B: The reduction rate of luminance is more than 15% and also 20% or less with respect to the initial luminance

C: Relative to the initial brightness, the reduction rate of brightness is greater than 20%

(2) Long-term reliability test

The manufactured LED was operated for 500 hours while supplying a current of 30 mA under the conditions of 85° C. and a relative humidity of 85%. Subsequently, the reduction rate of the luminance after the running compared to the initial luminance before the running was measured, and evaluated according to the following criteria.

<Evaluation criteria>

A: The reduction rate of luminance is 5% or less from the initial luminance

B: Relative to the initial brightness, the reduction rate of brightness is more than 5% and not more than 7%

C: Relative to the initial brightness, the reduction rate of brightness is greater than 7%

Example 1

The curable composition capable of being cured by hydrosilylation is obtained by making compounds represented by formulas A to E (blended amounts: formula A: 70 g, formula B: 200 g, formula C: 20 g, formula D: 50 g and formula E: 4g) prepared by mixing. Here, the polyorganosiloxane of formula A is obtained by reacting a mixture of octamethylcyclotetrasiloxane and octaphenylcyclotetrasiloxane with divinyltetramethyldisiloxane in a catalyst such as tetramethylhydrogen It is prepared by reacting at about 115°C for about 20 hours in the presence of ammonium oxide (TMAH). Subsequently, cyclic compounds with a molecular weight of not more than 800 (including compounds of formula 6, wherein R ^a and R ^b are methyl, R ^c is phenyl, and m and n are each in the range of 0 to 4) measured by GPC and m+n in the range of 1 to 8) was designed to be about 7% by a known purification method, and used to prepare a curable composition. Compounds other than the polyorganosiloxanes of formula A are prepared by known synthetic methods. Subsequently, the catalyst (platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane) was blended into the composition at a Pt(0) content of 10 ppm and uniformly Mix to prepare a curable composition.

[Formula A]

(ViMe ₂ SiO _1/2 ) ₂ (Me ₂ SiO _2/2 ) ₁₈ (Ph ₂ SiO _2/2 ) ₁₄

[Formula B]

(ViMe ₂ SiO _1/2 ) ₂ (MePhSiO _2/2 ) _0.1 (PhSiO _3/2 ) ₆

[Formula C]

(HMe ₂ SiO _1/2 ) ₂ (MePhSiO _2/2 ) _1.5

[Formula D]

(HMe ₂ SiO _1/2 ) ₂ (Ph ₂ SiO _2/2 ) _1.5

[Formula E]

(ViMe ₂ SiO _1/2 ) ₂ (EpSiO _3/2 ) ₃ (MePhSiO _2/2 ) ₂₀

Example 2

A curable composition was prepared by the same method as described in Example 1. However, in the case of the polyorganosiloxane of formula A, cyclic compounds having a molecular weight of not more than 800 as measured by GPC (including compounds of formula 6, wherein both R ^a and R ^b are methyl, R ^c is phenyl, The weight ratio of m and n each being 0 to 4 and m+n being 1 to 8) is designed to be about 5% by a post-synthesis purification method.

Example 3

A curable composition was prepared by the same method as described in Example 1. However, in the case of polyorganosiloxanes of formula A, cyclic compounds with a molecular weight of 800 or less as measured by GPC (including compounds of formula 6 in which both R ^a and R ^b are methyl and R ^c is phenyl , m and n are each 0 to 4 and m+n is 1 to 8) the weight ratio is designed to be about 2% by a post-synthesis purification method.

Example 4

The curable composition capable of being cured by hydrosilylation is obtained by making compounds represented by formulas F, B, D, and E (blend amounts: formula F: 70 g, formula B: 200 g, formula D: 70 g, and formula E: 4 g ) prepared by mixing. Here, the polyorganosiloxane of formula F is obtained by reacting a mixture of octamethylcyclotetrasiloxane and octaphenylcyclotetrasiloxane with divinyltetramethyldisiloxane in a catalyst such as tetramethylhydroxide It is prepared by reacting at about 115°C for 20 hours in the presence of ammonium trimethylammonium (TMAH). Subsequently, cyclic compounds with a molecular weight of not more than 800 (including compounds of formula 6, wherein R ^a and R ^b are methyl, R ^c is phenyl, and m and n are each in the range of 0 to 4) measured by GPC And m+n is in the range of 1 to 8) the weight ratio is designed to be about 2% by a known purification method, and used to prepare a curable composition. Compounds other than polyorganosiloxanes of formula F are prepared by known synthetic methods. Subsequently, the catalyst (platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane) was blended into the composition at a Pt(0) content of 10 ppm and uniformly Mix to prepare a curable composition.

[Formula F]

(ViMe ₂ SiO _1/2 ) ₂ (Me ₂ SiO _2/2 ) ₁₄ (Ph ₂ SiO _2/2 ) ₁₆

[Formula B]

(ViMe ₂ SiO _1/2 ) ₂ (MePhSiO _2/2 ) _0.1 (PhSiO _3/2 ) ₆

[Formula D]

(HMe ₂ SiO _1/2 ) ₂ (Ph ₂ SiO _2/2 ) _1.5

[Formula E]

(ViMe ₂ SiO _1/2 ) ₂ (EpSiO _3/2 ) ₃ (MePhSiO _2/2 ) ₂₀

Comparative example 1

The curable composition capable of being cured by hydrosilylation is obtained by making compounds represented by formulas G, B, C, D and E (blend amount: formula G: 70 g, formula B: 200 g, formula C: 20 g, formula D : 50g and formula E: 4g) prepared by mixing. Here, the polyorganosiloxane of formula G is obtained by reacting a mixture of octamethylcyclotetrasiloxane and tetramethyltetraphenylcyclotetrasiloxane with divinyltetramethyldisiloxane in a catalyst such as tetra Prepared in the presence of methylammonium hydroxide (TMAH). Subsequently, cyclic compounds with a molecular weight not greater than 800 measured by GPC (excluding the compound of formula 6; but including the compound of the following formula 6, wherein both R ^a and R ^b are methyl, and one of the two R ^c is benzene group, another R ^c is a methyl group, m and n are each in the range of 0 to 4 and m+n is in the range of 1 to 8) the weight ratio is designed to be about 7% by known purification methods, and used for the preparation curable composition. Compounds other than polyorganosiloxanes of formula G are prepared by known synthetic methods. Subsequently, the catalyst (platinum(0)-1,3-divinyl-1,1,3,3-tetramethyldisiloxane) was blended into the composition at a Pt(0) content of 10 ppm and uniformly Mix to prepare a curable composition.

[Formula G]

(ViMe ₂ SiO _1/2 ) ₂ (Me ₂ SiO _2/2 ) ₄ (MePhSiO _2/2 ) ₂₀

[Formula B]

(ViMe ₂ SiO _1/2 ) ₂ (MePhSiO _2/2 ) _0.1 (PhSiO _3/2 ) ₆

[Formula C]

(HMe ₂ SiO _1/2 ) ₂ (MePhSiO _2/2 ) _1.5

[Formula D]

(HMe ₂ SiO _1/2 ) ₂ (Ph ₂ SiO _2/2 ) _1.5

[Formula E]

(ViMe ₂ SiO _1/2 ) ₂ (EpSiO _3/2 ) ₃ (MePhSiO _2/2 ) ₂₀

Comparative example 2

A curable composition was prepared by the same method as described in Example 1. However, in the case of the polyorganosiloxane of formula A, cyclic compounds having a molecular weight of not more than 800 as measured by GPC (including compounds of formula 6, wherein both R ^a and R ^b are methyl, R ^c is phenyl, The weight ratio of m and n each being 0 to 4 and m+n being 1 to 8) is designed to be about 15% by a post-synthesis purification method.

The physical properties measured about Examples and Comparative Examples are summarized and shown in Table 1.

[Table 1]

Sulfur Exposure Test long-term reliability Example 1 B B Example 2 B A Example 3 B A Example 4 A A Comparative example 1 C B Comparative example 2 B C

Claims (16)

1. A curable composition comprising: A polymerization product comprising a polyorganosiloxane having a functional group comprising an aliphatic unsaturated bond, and a cyclic compound comprising a compound represented by Formula 6 and the cyclic compound a weight average molecular weight of 800 or less, and a content of the cyclic compound in the polymerization product of 7% by weight or less; and Silicon compounds comprising hydrogen atoms bonded to silicon atoms, [Formula 6] Wherein R ^a and R ^b are each independently an epoxy group or a monovalent hydrocarbon group, R ^c is an aryl group, m is 0 to 10, n is 0 to 10, and the sum (m+n) of m and n is 2 to 20. ^2. The curable composition of claim 1, wherein Ra and ^Rb are each independently alkyl. 3. The curable composition of claim 1, wherein the polyorganosiloxane comprises units of formula 2 and units of formula 3: [Formula 2] (R ¹ R ² SiO _2/2 ) [Formula 3] (R ³ ₂ SiO _2/2 ) Wherein, R ¹ and R ² are each independently an epoxy group or a monovalent hydrocarbon group, and R ³ is an aryl group. 4. The curable composition according to claim 1, wherein a molar ratio of aryl groups relative to all functional groups in the polyorganosiloxane is 30% to 60%. 5. The curable composition according to claim 3, wherein a ratio of the siloxane unit of Formula 2 in the polyorganosiloxane relative to the aryl group-containing bifunctional siloxane unit is 70% or more. 6. The curable composition according to claim 1, wherein the cyclic compound has a weight average molecular weight of 750 or less. 7. The curable composition of claim 1, wherein the polyorganosiloxane has an average empirical formula of Formula 4: [Formula 4] (R ⁴ ₃ SiO _1/2 ) _a (R ⁴ ₂ SiO _2/2 ) _b (R ⁴ SiO _3/2 ) _c (SiO _4/2 ) _d Wherein R ⁴ are each independently an epoxy group or a monovalent hydrocarbon group, provided that at least one of R ⁴ is an alkenyl group and at least one of R ⁴ is an aryl group; a is a positive number, b is a positive number, and c is 0 or a positive number, d is 0 or a positive number, and b/(b+c+d) is 0.7 to 1. 8. The curable composition of claim 1, wherein the polyorganosiloxane has an average empirical formula of Formula 5: [Formula 5] (R ⁵ R ⁶ ₂ SiO _1/2 ) _e (R ⁷ R ⁸ SiO _2/2 ) _f (R ⁹ ₂ SiO _2/2 ) _g (R ¹⁰ SiO _3/2 ) _h Wherein ^R5 is a monovalent hydrocarbon group, ^R6 is an alkyl group with 1 to 4 carbon atoms, ^R7 and ^R8 are each independently an alkyl group, an alkenyl group or an aryl group, ^R9 is an aryl group, and e is a positive number , f, g and h are each 0 or a positive number, and (f+g)/(f+g+h) is 0.7 to 1. 9. The curable composition according to claim 1, wherein the polymerization product is a polymerization product comprising a mixture of compounds represented by formula 7: [Formula 7] wherein R ^d and R ^e are each independently an epoxy group or a monovalent hydrocarbon group, and o is 3 to 6. 10. The curable composition of claim 1, wherein the polymerization product is a polymerization product comprising a mixture of a compound of formula 8 and a compound of formula 9: [Formula 8] [Formula 9] wherein each of R ^f and R ^g is an epoxy group or an alkyl group, each of R ^h and R ⁱ is an epoxy group or an aryl group, p is a number from 3 to 6, and q is a number from 3 to 6. 11. A curable composition according to claim 9 or claim 10, wherein the mixture further comprises a polyorganosiloxane having the average empirical formula of Formula 10 or Formula 11: [Formula 10] [R ^j SiO _3/2 ] [Formula 11] [R ^k R ¹ ₂ SiO _1/2 ] _p [R ^m SiO _3/2 ] _q wherein R ^j , R ^k and R ^m are each independently an epoxy group or a monovalent hydrocarbon group, R ¹ is an alkyl group having 1 to 4 carbon atoms, p is 1 to 3 and q is 1 to 10. 12. The curable composition of claim 1 , further comprising a polyorganosiloxane having the average empirical formula of Formula 13: [Formula 13] (R ¹¹ ₃ SiO _1/2 ) _a (R ¹¹ ₂ SiO _2/2 ) _b (R ¹¹ Si(O _3/2 ) _e (SiO _4/2 ) _d Wherein R ¹¹ are each independently an epoxy group or a monovalent hydrocarbon group, provided that at least one of R ¹¹ is an alkenyl group and at least one of R ¹¹ is an aryl group; a is a positive number, and b is 0 or a positive number, c is a positive number, d is 0 or a positive number, b/(b+c+d) is less than 0.65, and c/(c+d) is 0.8 or more. 13. The curable composition of claim 1 , further comprising a compound of formula 14 or a compound having the average empirical formula of formula 15: [Formula 14] R ¹² ₃ SiO(R ¹² ₂ SiO) _n siR ¹² ₃ [Formula 15] (R ¹³ ₃ SiO _1/2 ) _a (R ¹³ ₂ SiO _2/2 ) _b (R ¹³ SiO _3/2 ) _e (SiO ₂ ) _d wherein R ¹² are each independently hydrogen or a monovalent hydrocarbon group, provided that at least two of R ¹² are hydrogen atoms and at least one of R ¹² is an aryl group; n is 1 to 100; each R ¹³ is independently hydrogen or a monovalent hydrocarbon group, provided that at least two of R ¹³ are hydrogen atoms and at least one of R ¹³ is an aryl group; and a is a positive number, b is 0 or a positive number, c is a positive number, and d is 0 or a positive number. 14. An optical semiconductor encapsulated by a cured curable composition according to claim 1. 15. A liquid crystal display comprising the optical semiconductor according to claim 14 in a backlight unit. 16. A lighting device comprising an optical semiconductor according to claim 14.